EP1474378A1 - Method for the production of amines - Google Patents

Method for the production of amines

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Publication number
EP1474378A1
EP1474378A1 EP03714720A EP03714720A EP1474378A1 EP 1474378 A1 EP1474378 A1 EP 1474378A1 EP 03714720 A EP03714720 A EP 03714720A EP 03714720 A EP03714720 A EP 03714720A EP 1474378 A1 EP1474378 A1 EP 1474378A1
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EP
European Patent Office
Prior art keywords
catalysts
hydrogenation
carried out
catalyst
bar
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EP03714720A
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German (de)
French (fr)
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EP1474378B1 (en
Inventor
Dominic Vanoppen
Ekkehard Schwab
Frederik Van Laar
Hartwig Voss
Steffen OEHLENSCHLÄGER
Wolfgang Mackenroth
Konrad Morgenschweis
Ulrich Penzel
Bernd Weidner
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation

Definitions

  • the invention relates to a continuous process for the preparation of amines, in particular aromatic amines, by catalytic hydrogenation of the nitro compounds on which the amines are based.
  • the compound to be reduced is mixed with the catalyst in a solvent and reduced batchwise in an autoclave or continuously in a loop reactor, a bubble column or a reactor cascade.
  • a number of disadvantages with these previously known methods e.g. the need to discharge and in particular to discharge deactivated catalyst components, which leads to catalyst losses.
  • the frequently occurring side reactions which lead to the formation of interfering substances, e.g. tar-like constituents, and thus lead to yield reductions, are a problem of many processes used to date.
  • EP-A-634 391 describes a process for the hydrogenation of aromatic polynitro compounds to amines in which, by means of technological optimization using a loop venturi reactor with an ejector, coupled with special conditions such as an exact circulation volume ratio, an exact energy input, a precisely set one Hydrogen volume flow, the problems mentioned hydrogenation of aromatic polynitro compounds to be minimized.
  • Known hydrogenation catalysts are used as catalysts, preferably metals of subgroup VIII of the periodic table and in particular Raney iron, cobalt and nickel being used.
  • WO 00/35852 describes a process for the preparation of amines by hydrogenation of nitro compounds.
  • the reaction is carried out in a vertical reactor with a jet nozzle pointing downwards, through which the starting materials and the reaction mixture are fed, an external circuit through which the reaction mixture is fed to the jet nozzle, and a flow reversal at the lower end of the reactor.
  • the end product is preferably discharged via a separation unit for the catalyst.
  • Settiers, filter units or centrifuges are proposed as separation units.
  • the selectivity and the space-time yield in hydrogenations can be increased significantly.
  • a further improvement of the process is desirable for industrial hydrogenation.
  • the complete separation of the hydrogenation catalysts used is of crucial importance for the economy of the process.
  • Complete separation of the catalyst from the reaction mixture discharged from the reactor simplifies the work-up of the end product.
  • the separated catalyst can be returned to the reactor and therefore does not need to be replaced by fresh catalyst. This is particularly important when using noble metal catalysts.
  • the object of the invention was to develop a process for the separation of catalysts in the hydrogenation of nitroaromatics to aromatic amines, which allows complete and gentle separation of the catalysts and in which the separated catalyst can be completely recycled from the separation stage back into the reactor.
  • the task was surprisingly achieved by separating the catalyst by means of a crossflow filter which is designed as a membrane filter, the membrane filtration at a pressure on the suspension side of 5 to 50 bar, preferably 10 to 30 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flow velocity on the suspension side of 1 to 6 m / s is carried out.
  • a crossflow filter which is designed as a membrane filter
  • the invention thus relates to a process for the preparation of amines by catalytic hydrogenation of nitroaromatics and subsequent removal of the catalysts from the reaction mixture containing at least one aromatic amine and water, characterized in that the removal of the catalysts is carried out by means of membrane filtration, the membrane filtration at a pressure on the suspension side of 5 to 50 bar, preferably 10 to 30 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flow rate on the suspension side of 1 to 6 m / s.
  • the suspension side is understood to mean the side of the membrane filter on which the catalyst-containing mixture is located;
  • the permeate side is understood to mean the side of the membrane filter on which the catalyst-free mixture is located. 5
  • the discharge from the hydrogenation reactor is brought into contact with a membrane under pressure and permeate (filtrate) on the back of the membrane at a
  • a catalyst concentrate (retentate) is obtained, which can be returned to the synthesis reactor without further work-up, and a practically catalyst-free permeate, which
  • the filtration according to the invention can be carried out continuously or batchwise.
  • the reaction mixture is passed over a membrane filter after the reaction. This embodiment is less preferred because it is the separated one
  • the filter membranes used for the process according to the invention preferably have pore diameters in the range between 40 10 nm and 20 ⁇ m, in particular in the range between 50 nm and 10 ⁇ m and preferably between 100 nm and 5 ⁇ m.
  • the separating layers of the filter membranes can consist of organic polymers, ceramics, metal, carbon or combinations thereof and must be stable in the reaction medium and at the process temperature.
  • the separating layers are usually on one or more layers porous substructure, which consists of the same or at least one different material as the separating layer, applied.
  • inorganic membranes are preferred. Examples are separating layers made of metal and substructures made of metal, separating layers made of ceramic and substructures made of metal, ceramic or carbon, separating layers made of polymers and substructures made of polymer, metal, ceramic or ceramic on metal. For example, ⁇ -Al 2 0 3 , ⁇ -Al 2 0 3 ,
  • Zr0 2 , Ti0, SiC or mixed ceramic materials are used.
  • polymers used are polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polysulfone, polyether sulfone, polyether ether ketone and polyamide.
  • the membranes are usually used in pressure-resistant housings that allow the separation between retentate (containing catalyst) and permeate (catalyst-free filtrate) under the pressure conditions required for the filtration.
  • the housings can be in flat, tubular, multi-channel, capillary or
  • Winding geometry are carried out, for the corresponding pressure housing, which allow a separation between retentate and the permeate, are available.
  • a filter element can contain several channels. Furthermore, several of these elements can be combined into one module in one housing.
  • metal membranes are used which are welded to the housings.
  • the optimal transmembrane pressures between retentate and permeate are essentially dependent on the diameter of the membrane pores, the hydrodynamic conditions that influence the top layer structure and the mechanical stability of the membrane at the operating temperature, depending on the membrane type, at least 0.3 bar. in particular between 0.5 and 50 bar, preferably 1 to 25 bar. Higher transmembrane pressures mostly lead to higher permeate flows. Since the synthesis discharge is mostly fed directly to the membrane filtration stage with the synthesis pressure, the transmembrane pressure can be reduced to a value which is lower than the synthesis pressure by increasing the permeate pressure.
  • the membrane Since the synthesis temperature is determined by the process and is above 80 ° C, the membrane must be stable at this temperature. In principle, higher temperatures lead to higher permeate flows and are therefore preferred.
  • reaction mixture has to be cooled before the filtration and the retentate has to be heated again before being fed into the reactor. This embodiment is not preferred.
  • the permeate flows that can be achieved depend heavily on the membrane type and geometry used, on the process conditions, on the suspension composition, on the catalyst concentration and on the catalyst type.
  • the rivers are usually between 20 and 500 kg / m2 / h.
  • a catalyst retention> 99% can be achieved by the process according to the invention.
  • All of the catalysts which can be used for the hydrogenation of nitroaromatics can be separated off by the process according to the invention.
  • Suitable catalysts are metals of subgroup VIII of the periodic table, which can be applied to support materials such as carbon or oxides of aluminum, silicon or other materials.
  • Raney nickel and / or supported catalysts based on nickel, palladium, iridium and / or platinum on carbon supports are preferably used.
  • the process can be used particularly advantageously for the separation of catalysts on which little of the highly condensed by-products obtained as a by-product in the hydrogenation, often referred to as "tar", is obtained. This tar can lead to blockages in the membrane used and reduce the service life of the filter.
  • the average grain size of the catalysts used is usually in the range between 10 nm and 200 ⁇ m, in particular in the range between 50 nm and 100 ⁇ m and preferably between 100 nm and 30 ⁇ m.
  • the aromatic nitro compounds can be hydrogenated by customary and known processes.
  • the mono- and / or polynitro compound can be used in pure form, as a mixture with the corresponding mono- and / or polyamine, as a mixture with the corresponding mono- and / or polyamine and water or as a mixture with the corresponding mono- and / or polyamine, water and a particularly alcoholic solvent.
  • the aromatic mono- and / or poly-nitro compound is introduced into the mixture in finely divided form.
  • the reaction mixture which leaves the reactor contains water which is formed as a by-product of the hydrogenation.
  • the reactors used are those for the customary and known hydrogenation reactors. Examples of this are stirred tanks, bubble columns, which can contain packings, or loop reactors, such as loop venturi reactors, or jet loop reactors with internal and external circuits, as described, for example, in WO 00/35852.
  • the process according to the invention for separating catalysts can be used particularly advantageously when using loop reactors with an external circuit.
  • the membrane filter is arranged in the outer circuit.
  • a hydrogenation reactor is used, as described in WO 00/35852.
  • an additional pump for membrane filtration can be dispensed with, since the pump for the external circuit can maintain the necessary pressure on the suspension side. This can significantly simplify the process.
  • complete conversion of the nitroaromatics is possible, so that the subsequent workup is particularly simple after the catalyst has been completely removed.
  • the advantages of precious metal catalysts especially those on the Basis of platinum, palladium and / or iridium, namely the high activity and the good selectivity, especially for wearing.
  • Aromatic nitrove compounds having one or more nitro groups and 6 to 18 carbon atoms for example nitrobenzenes, such as o-, m-, p-nitrobenzene, 1,3-dinitrobenzene, nitrotoluenes, such as e.g. 2,4-, 2,6-dinitrotoluene, 2,4,4-trinitrotoluene, nitroxylenes, e.g.
  • nitronaphthalenes such as, for example 1-, 2-nitronaphthalene, 1,5 and 1,8-dinitronaphthalene, chloronitrobenzenes, e.g.
  • Aromatic nitro compounds preferably mononitrobenzene, methylnitrosupenzene or methylnitrotoluene, and in particular 2,4-dinitro-toluene or its technical mixtures with 2,6-dinitrotoluene, are preferred according to the process of the invention, these mixtures preferably up to 35 percent by weight, based on the The total mixture, comprising 2, 6-dinitrotoluene with 1 to 4 percent of vicinal DNT and 0.5 to 1.5% of 2,5- and 3,5-dinitrotoluene, is hydrogenated to the corresponding amines.
  • Dinitrotoluene was hydrogenated on a supported nickel catalyst with an average particle size of 5 to 10 ⁇ m at 25 bar and 120 ° C in a 5-1 jet loop reactor with circulation pump, nozzle, plug-in pipe and heat exchanger.
  • the activity of the catalyst was continuously monitored using gas chromatography samples and, if necessary, catalyst was added.
  • the Concentration of the catalyst was 3% by weight, based on the reaction mixture.
  • the catalyst could be separated from the reaction mixture either with a membrane filter (according to the invention) or with a settier (comparison).
  • a cylinder made of highly porous ceramic with a length of 750 mm contained a longitudinal channel with a diameter of 6 mm, on the surface of which the actual filter-effective membrane made of zirconium dioxide with a pore size of 50 nm was applied.
  • the suspension to be treated flowed at a flow rate of 4 m / s in the channel along the membrane, a partial stream passing through the membrane as permeate and being discharged through the ceramic carrier material.
  • the transmembrane pressure was 2 bar, the permeate flow was 440 l / m 2 / h.
  • a partial flow of the circulation flow was branched off with the admission pressure of the circulation pump into the lower part of a settier and from there was quantity-controlled and fed back into the reactor without additional conveying device.
  • the actual reactor discharge (settler discharge) flowed upwards through a separator pipe inclined by 55 ° and, controlled by the liquid level or gas content in the reactor, was discharged via an expansion valve.
  • the flow conditions in the separator lamella were set in such a way that all particles larger than 1 ⁇ m were separated and sank into the settling sump, where they were transported back into the reactor with the recycle stream (settler return). Smaller particles were removed with the end product.
  • Example 1 The devices for hydrogenation and catalyst separation described in Example 1 were used and the effectiveness of different catalysts at different reaction temperatures in the hydrogenation of nitrobenzene was tested.
  • the catalyst from Example 1 was used in a concentration of 2% by weight, based on the reaction mixture.
  • the transmembrane pressure was 1 bar, the permeate flow was 200 l / m 2 / h.
  • a catalyst consisting of 5% by weight of platinum and 2% by weight of iron on activated carbon with an average particle size of 20 to 30 ⁇ m in a concentration of 2% by weight, based on the reaction mixture, was used.
  • the transmembrane pressure was 1 bar, the permeate flow was 200 l / m 2 / h.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides a process for preparing amines by catalytic hydrogenation of nitroaromatics and subsequent removal of the catalysts from the reaction mixture, which contains at least one aromatic amine and water, which comprises carrying out the removal of the catalysts by means of membrane filtration, which is carried out at a pressure on the suspension side of from 5 to 50 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flux rate on the suspension side of from 1 to 6 m/s.

Description

Verfahren zur Herstellung von AminenProcess for the production of amines
BesehreibungBesehreibung
Die Erfindung betrifft ein kontinuierliches Verfahren zur Herstellung von Aminen, insbesondere aromatischen Aminen, durch katalytische Hydrierung der den Aminen zugrunde liegenden Nitro- verbindungen.The invention relates to a continuous process for the preparation of amines, in particular aromatic amines, by catalytic hydrogenation of the nitro compounds on which the amines are based.
Die Herstellung von Aminen, insbesondere von aromatischen Mono- und/oder Polya inen durch katalytische Hydrierung der entsprechenden Mono- und/oder Polynitroverbindungen ist seit langem bekannt und vielfach in der Literatur beschrieben.The production of amines, in particular aromatic mono- and / or polya inen by catalytic hydrogenation of the corresponding mono- and / or polynitro compounds has long been known and has been described many times in the literature.
Bei der in der Technik üblichen Herstellung der aromatischen Mono- und/oder Polyamine durch Umsetzung von Nitroverbindungen mit Wasserstoff wird eine beträchtliche Wärmemenge frei. Zumeist wird die Hydrierung daher in der Technik bei möglichst niedrigen Temperaturen unter Einsatz von Hydrierkatalysatoren in derA considerable amount of heat is released in the production of the aromatic mono- and / or polyamines customary in industry by reacting nitro compounds with hydrogen. Usually, the hydrogenation is therefore carried out in technology at the lowest possible temperatures using hydrogenation catalysts in the
Flüssigphase durchgeführt. Dabei wird die zu reduzierende Verbindung in einem Lösungsmittel mit dem Katalysator vermischt und diskontinuierlich in einem Autoklaven oder kontinuierlich in einem Schlaufenreaktor, einer Blasensäule oder einer Reaktor- kaskade reduziert. Bei diesen bisher bekannten Verfahren gibt es eine Reihe von Nachteilen, wie z.B. die Notwendigkeit des Austragens und besonders des Ausschleusens desaktivierter Katalysatoranteile, was zu Katalysatorverlusten führt. Ferner stellen die häufig auftretenden Nebenreaktionen, die zur Bildung störender Substanzen, wie z.B. teerartiger Bestandteile, und damit zu Ausbeuteminderungen führen, ein Problem vieler bislang verwendeter Verfahren dar.Liquid phase carried out. The compound to be reduced is mixed with the catalyst in a solvent and reduced batchwise in an autoclave or continuously in a loop reactor, a bubble column or a reactor cascade. There are a number of disadvantages with these previously known methods, e.g. the need to discharge and in particular to discharge deactivated catalyst components, which leads to catalyst losses. Furthermore, the frequently occurring side reactions which lead to the formation of interfering substances, e.g. tar-like constituents, and thus lead to yield reductions, are a problem of many processes used to date.
In EP-A-634 391 wird ein Verfahren zur Hydrierung von aromatischen Polynitroverbindungen zu Aminen beschrieben, in dem durch technologische Optimierung unter Einsatz eines Loop- Venturi-Reaktors mit einem Ejektor, gekoppelt mit speziellen Bedingungen wie genauem Umwälzvolumenverhältnis, genauem Energieeintrag, einem genau eingestellten Wasserstoffvolumenstrom, die genannten Probleme der Hydrierung von aromatischen Polynitroverbindungen minimiert werden sollen. Als Katalysatoren werden bekannte Hydrierkatalysatoren verwendet, wobei vorzugsweise Metalle der VIII. Nebengruppe des Periodensystems und insbesondere Raney-Eisen, -Kobalt und -Nickel eingesetzt werden. Bei diesem Verfahren kann es, bedingt durch die Anordnung eines Wärmetauschers zur Abführung der Reaktionswärme außerhalb des Schlaufenreaktors, im Ejektor und im Reaktor zu örtlichen Überhitzungen mit sofortigem Einsetzen von Nebenreaktionen wie Kern- hydrierungen, hydrogenolytischen Spaltungen bzw. Bildung von hochmolekularen, teerartigen Produkten, die die Katalysatoroberfläche belegen, kommen. Darüber hinaus stellt sich im Reaktorvolumen außerhalb des Ejektors eine bezüglich des Strömungsund Verweilzeitverhaltens reine Blasensäulencharakteristik ein, in dem regellose klein- und großräumige Wirbel mit vergleichsweise geringer StoffÜbergangsleistung auftreten. Eine wesentliche Verbesserung der Hydrierausbeute, der Hydrierselektivität und der Raum-Zeit-Ausbeute wird somit bei diesem Verfahren kaum erreicht . Außerdem wird auch hier durch das Umpumpen der gesamten Reaktionsmischung der Katalysator mechanisch stark beansprucht, was wiederum zu einer verminderten Standzeit des Katalysators führt .EP-A-634 391 describes a process for the hydrogenation of aromatic polynitro compounds to amines in which, by means of technological optimization using a loop venturi reactor with an ejector, coupled with special conditions such as an exact circulation volume ratio, an exact energy input, a precisely set one Hydrogen volume flow, the problems mentioned hydrogenation of aromatic polynitro compounds to be minimized. Known hydrogenation catalysts are used as catalysts, preferably metals of subgroup VIII of the periodic table and in particular Raney iron, cobalt and nickel being used. In this method, due to the arrangement of a heat exchanger for removing the heat of reaction outside the loop reactor, local overheating in the ejector and in the reactor with immediate onset of side reactions such as nuclear hydrogenation, hydrogenolytic cleavage or formation of high-molecular, tar-like products occupy the catalyst surface. In addition, in the reactor volume outside the ejector, a bubble column characteristic that is pure with regard to the flow and residence time behavior arises, in which irregular small and large-area vortices occur with a comparatively low mass transfer rate. A significant improvement in the hydrogenation yield, the hydrogenation selectivity and the space-time yield is thus hardly achieved in this process. In addition, the pumping of the entire reaction mixture places a heavy mechanical load on the catalyst, which in turn leads to a reduced service life of the catalyst.
In WO 00/35852 wird ein Verfahren zur Herstellung von Aminen durch Hydrierung von Nitroverbindungen beschrieben. Bei diesem Verfahren wird die Reaktion in einem vertikalen Reaktor mit einer nach unten gerichteten Strahldüse, über die die Edukte sowie das Reaktionsgemisch zugeführt werden, einen äußeren Kreislauf, über den das Reaktionsgemisch der Strahldüse zugeführt wird, sowie einer Strömungsumkehr am unteren Ende des Reaktors durchgeführt. Der Austrag des Endprodukts erfolgt vorzugsweise über eine Abtrenneinheit für den Katalysator. Als Abtrenneinheit werden beispielsweise Settier, Filtereinheiten, oder Zentrifugen vorgeschlagen.WO 00/35852 describes a process for the preparation of amines by hydrogenation of nitro compounds. In this process, the reaction is carried out in a vertical reactor with a jet nozzle pointing downwards, through which the starting materials and the reaction mixture are fed, an external circuit through which the reaction mixture is fed to the jet nozzle, and a flow reversal at the lower end of the reactor. The end product is preferably discharged via a separation unit for the catalyst. Settiers, filter units or centrifuges are proposed as separation units.
Mit diesem Verfahren kann die Selektivität und die Raum-Zeit- Ausbeute bei Hydrierungen deutlich gesteigert werden. Für die großtechnische Hydrierung ist jedoch eine weitere Verbesserung des Verfahrens wünschenswert. Insbesondere die möglichst voll- ständige Abtrennung der eingesetzten Hydrierkatalysatoren ist für die Wirtschaftlichkeit des Verfahrens von entscheidender Bedeutung. Eine vollständige Abtrennung des Katalysators von der aus dem Reaktor ausgeschleusten Reaktionsmischung vereinfacht die Aufarbeitung des Endprodukts . Der abgetrennte Katalysator kann dem Reaktor wieder zugeführt werden und braucht somit nicht durch frischen Katalysator ersetzt werden. Dies ist insbesondere bei der Verwendung von Edelmetallkatalysatoren von Bedeutung.With this method, the selectivity and the space-time yield in hydrogenations can be increased significantly. However, a further improvement of the process is desirable for industrial hydrogenation. In particular, the complete separation of the hydrogenation catalysts used is of crucial importance for the economy of the process. Complete separation of the catalyst from the reaction mixture discharged from the reactor simplifies the work-up of the end product. The separated catalyst can be returned to the reactor and therefore does not need to be replaced by fresh catalyst. This is particularly important when using noble metal catalysts.
Es ist bekannt, Katalysatoren mittels einer Querstromfiltration abzutrennen. Diese Art der Abtrennung führt zu einer besonders schonenden Abtrennung des Katalysators . In DE 32 45 318 wird die Abtrennung von Katalysatoren bei Gas/Flüssigreaktionen mittels eines nach dem Querstromprinzip betriebenen Mikrofilters durchgeführt. Um die Beanspruchung des Katalysators gering zu halten, wird die Filtration bei Betriebsdrücken von mindestens 10 bar auf der Suspensionsseite und Differenzdrücken zwischen Suspensions- und Filtratseite von höchstens 6 bar sowie Temperaturen im Bereich zwischen 80 und 200°C betrieben.It is known to separate catalysts by means of cross-flow filtration. This type of separation leads to a particularly gentle separation of the catalyst. In DE 32 45 318, the separation of catalysts in gas / liquid reactions is carried out by means of a microfilter operated according to the crossflow principle. In order to keep the stress on the catalyst low, the filtration is operated at operating pressures of at least 10 bar on the suspension side and differential pressures between the suspension and filtrate side of at most 6 bar and temperatures in the range between 80 and 200 ° C.
In DE 30 40 631 wird die Entfernung von Katalysatoren ausDE 30 40 631 describes the removal of catalysts
Reaktionsmischungen mittels Membranfiltration beschrieben und erwähnt, dass dieses Verfahren auch bei der Hydrierung von Nitro- aromaten eingesetzt werden kann. Als Filter werden Hohlfasern eingesetzt. Die Filtration wird bei sehr niedrigen Temperaturen durchgeführt .Reaction mixtures described by means of membrane filtration and mentioned that this process can also be used in the hydrogenation of nitroaromatics. Hollow fibers are used as filters. The filtration is carried out at very low temperatures.
Aufgabe der Erfindung war es, ein Verfahren zur Abtrennung von Katalysatoren bei der Hydrierung von Nitroaromaten zu aromatischen Aminen zu entwickeln, das eine vollständige und schonende Abtrennung der Katalysatoren erlaubt und bei dem der abgetrennte Katalysator vollständig aus der Trennstufe wieder in den Reaktor zurückgeführt werden kann.The object of the invention was to develop a process for the separation of catalysts in the hydrogenation of nitroaromatics to aromatic amines, which allows complete and gentle separation of the catalysts and in which the separated catalyst can be completely recycled from the separation stage back into the reactor.
Die Aufgabe konnte überraschenderweise gelöst werden, indem die Abtrennung des Katalysators mittels eines Querstromfilters vorgenommen wird, der als Membranfilter ausgestaltet ist, wobei die Membranfiltration bei einem Druck auf der Suspensionsseite von 5 bis 50 bar, vorzugsweise 10 bis 30 bar, einer Druckdifferenz zwischen der Suspensionsseite und der Permeatseite von mindestens 0,3 bar und einer Strömungsgeschwindigkeit auf der Suspensionsseite von 1 bis 6 m/s durchgeführt wird.The task was surprisingly achieved by separating the catalyst by means of a crossflow filter which is designed as a membrane filter, the membrane filtration at a pressure on the suspension side of 5 to 50 bar, preferably 10 to 30 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flow velocity on the suspension side of 1 to 6 m / s is carried out.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von Aminen durch katalytische Hydrierung von Nitroaromaten und nachfolgende Abtrennung der Katalysatoren aus dem Reaktions- gemisch, enthaltend mindestens ein aromatisches Amin und Wasser, dadurch gekennzeichnet, dass die Abtrennung der Katalysatoren mittels Membranfiltration erfolgt, wobei die Membranfiltration bei einem Druck auf der Suspensionsseite von 5 bis 50 bar, vorzugsweise 10 bis 30 bar, einer Druckdifferenz zwischen der Suspensionsseite und der Permeatseite von mindestens 0,3 bar und einer Strömungsgeschwindigkeit auf der Suspensionsseite von 1 bis 6 m/s durchgeführt wird. Unter Suspensionsseite wird die Seite des Membranfilters verstanden, auf der sich die Katalysator enthaltende Mischung befindet, unter Permeatseite wird die Seite des Membranfilters verstanden, auf der sich die katalysatorfreie Mischung befindet. 5The invention thus relates to a process for the preparation of amines by catalytic hydrogenation of nitroaromatics and subsequent removal of the catalysts from the reaction mixture containing at least one aromatic amine and water, characterized in that the removal of the catalysts is carried out by means of membrane filtration, the membrane filtration at a pressure on the suspension side of 5 to 50 bar, preferably 10 to 30 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flow rate on the suspension side of 1 to 6 m / s. The suspension side is understood to mean the side of the membrane filter on which the catalyst-containing mixture is located; the permeate side is understood to mean the side of the membrane filter on which the catalyst-free mixture is located. 5
Zur Durchführung des erfindungsgemäßen Verfahrens und Gewinnung eines katalysatorfreien Produktstromes wird der Austrag aus dem Hydrierreaktor unter Druck mit einer Membran in Kontakt gebracht und Permeat (Filtrat) auf der Rückseite der Membran bei einemTo carry out the process according to the invention and to obtain a catalyst-free product stream, the discharge from the hydrogenation reactor is brought into contact with a membrane under pressure and permeate (filtrate) on the back of the membrane at a
10 geringeren Druck als auf der Seite, auf der sich das katalysator- haltige Reaktionsgemisch befindet, abgezogen. Man erhält ein Katalysatorkonzentrat (Retentat) , das ohne weitere Aufarbeitung in den Synthesereaktor zurückgeführt werden kann, und ein praktisch katalysatorfreies Permeat, welches das Umsetzung-10 lower pressure than on the side on which the catalyst-containing reaction mixture is located. A catalyst concentrate (retentate) is obtained, which can be returned to the synthesis reactor without further work-up, and a practically catalyst-free permeate, which
15 sprodukt, beim erfindungsgemäßen Verfahren das aromatische Amin, sowie Wasser und gegebenenfalls Lösungsmittel enthält.15 product, in the process according to the invention, the aromatic amine, and water and optionally solvent.
Die erfindungsgemäße Filtration kann kontinuierlich oder diskontinuierlich durchgeführt werden.The filtration according to the invention can be carried out continuously or batchwise.
2020
Bei der kontinuierlichen Durchführung des Verfahrens wird ständig zumindest ein Teilstrom des Reaktionsgemisches durch einen Membranfilter gefahren. Bei dieser Ausführungsform des erfindungsgemäßen Verfahrens ist es bevorzugt, den MembranfilterWhen the process is carried out continuously, at least a partial stream of the reaction mixture is continuously passed through a membrane filter. In this embodiment of the method according to the invention, it is preferred to use the membrane filter
25 in den externen Kreislauf eines Umlaufreaktors anzuordnen. Diese Ausführungsform des erfindungsgemäßen Verfahrens ist bevorzugt.25 to be arranged in the external circuit of a circulation reactor. This embodiment of the method according to the invention is preferred.
Bei der diskontinuierlichen Durchführung der erfindungsgemäßen Filtration wird das Reaktionsgemisch durch eine zuschaltbareWhen the filtration according to the invention is carried out batchwise, the reaction mixture is switched on by a switchable
30 Reinigungsstufe, bestehend aus Membranfilter und einer eigenen Zirkulationspumpe, geleitet. Bei einer anderen Ausgestaltung der diskontinuierlichen Filtration wird im Anschluss an die Reaktion das Reaktionsgemisch über einen Membranfilter gefahren. Diese Ausführungsform ist weniger bevorzugt, da hier der abgetrennte30 cleaning stage, consisting of a membrane filter and its own circulation pump. In another embodiment of the discontinuous filtration, the reaction mixture is passed over a membrane filter after the reaction. This embodiment is less preferred because it is the separated one
35 Katalysator höher aufkonzentiert werden uss .35 catalyst to be concentrated more uss.
Die für das erfindungsgemäße Verfahren eingesetzten Filtermembranen haben, abhängig von der Partikelgröße des eingesetzten Katalysators, vorzugsweise Porendurchmesser im Bereich zwischen 40 10 nm und 20 um, insbesondere im Bereich zwischen 50 nm und 10 μ und vorzugsweise zwischen 100 nm und 5 Um.Depending on the particle size of the catalyst used, the filter membranes used for the process according to the invention preferably have pore diameters in the range between 40 10 nm and 20 μm, in particular in the range between 50 nm and 10 μm and preferably between 100 nm and 5 μm.
Die Trennschichten der Filtermembranen können aus organischen Polymeren, Keramik, Metall, Kohlenstoff oder Kombinationen daraus 45 bestehen und müssen in dem Reaktionsmedium und bei der Prozesstemperatur stabil sein. Aus mechanischen Gründen sind die Trennschichten in der Regel auf einer ein- oder mehrschichtigen porösen Unterstruktur, die aus dem gleichen oder auch aus mindestens einem unterschiedlichen Material wie die Trennschicht besteht, aufgebracht. Bevorzugt sind wegen der hohen Synthesetemperatur und der damit hohen Temperatur der filtrierten Reaktionsmischung anorganische Membranen. Beispiele sind Trennschichten aus Metall und Unterstrukturen aus Metall, Trennschichten aus Keramik und Unterstrukturen aus Metall, Keramik oder Kohlenstoff, Trennschichten aus Polymeren und Unterstrukturen aus Polymer, Metall, Keramik oder Keramik auf Metall. Als Keramik werden beispielsweise α-Al203 , γ-Al203 ,The separating layers of the filter membranes can consist of organic polymers, ceramics, metal, carbon or combinations thereof and must be stable in the reaction medium and at the process temperature. For mechanical reasons, the separating layers are usually on one or more layers porous substructure, which consists of the same or at least one different material as the separating layer, applied. Because of the high synthesis temperature and the high temperature of the filtered reaction mixture, inorganic membranes are preferred. Examples are separating layers made of metal and substructures made of metal, separating layers made of ceramic and substructures made of metal, ceramic or carbon, separating layers made of polymers and substructures made of polymer, metal, ceramic or ceramic on metal. For example, α-Al 2 0 3 , γ-Al 2 0 3 ,
Zr02, Ti0 , SiC oder gemischte keramische Werkstoffe eingesetzt. Als Polymere werden beispielsweise Polytetrafluorethylen, Poly- vinylidenfluorid (PVDF) , Polysulfon, Polyethersulfon, Polyether- etherketon, Polyamid eingesetzt.Zr0 2 , Ti0, SiC or mixed ceramic materials are used. Examples of polymers used are polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polysulfone, polyether sulfone, polyether ether ketone and polyamide.
Die Membranen werden üblicherweise in druckfeste Gehäuse eingesetzt, welche die Trennung zwischen Retentat (katalysator- haltig) und Permeat (katalysatorfreies Filtrat) bei den für die Filtration erforderlichen Druckbedingungen erlauben. Die Gehäuse können in Flach-, Rohr-, Multikanalelement-, Kapillar- oderThe membranes are usually used in pressure-resistant housings that allow the separation between retentate (containing catalyst) and permeate (catalyst-free filtrate) under the pressure conditions required for the filtration. The housings can be in flat, tubular, multi-channel, capillary or
Wickelgeometrie ausgeführt werden, für die entsprechende Druckgehäuse, die eine Trennung zwischen Retentat und dem Permeat erlauben, verfügbar sind. Je nach Flächenbedarf kann ein Filterelement mehrere Kanäle enthalten. Weiterhin können mehrere dieser Elemente in einem Gehäuse zu einem Modul zusammengefasst werden.Winding geometry are carried out, for the corresponding pressure housing, which allow a separation between retentate and the permeate, are available. Depending on the area required, a filter element can contain several channels. Furthermore, several of these elements can be combined into one module in one housing.
In einer bevorzugten Ausführungsform werden Metallmembranen verwendet, die mit den Gehäusen verschweißt sind.In a preferred embodiment, metal membranes are used which are welded to the housings.
Es ist bevorzugt, das Verfahren so zu betreiben, dass sich möglichst keine Deckschichten auf der Suspensionsseite der Membran ausbilden. Falls sich störende Deckschichten ausbilden, durch die die Filtration beeinträchtigt wird, ist es möglich, diese durch Strömungsumkehr zwischen Suspensionsseite und Permeatseite zu entfernen. Die Strömungsumkehr kann insbesondere durch Anheben des Permeatdrucks über den Retentatdruck bewirkt werden.It is preferred to operate the method in such a way that, if possible, no cover layers form on the suspension side of the membrane. If disruptive cover layers are formed which affect the filtration, it is possible to remove them by reversing the flow between the suspension side and the permeate side. The flow reversal can be brought about in particular by raising the permeate pressure above the retentate pressure.
Die optimalen transmembranen Drücke zwischen Retentat und Permeat liegen im wesentlichen, abhängig von Durchmesser der Membran- poren, den hydro-dynamischen Bedingungen, die den Deckschichtaufbau beeinflussen, und der mechanischen Stabilität der Membran bei der Betriebstemperatur je nach Membranart bei mindestens 0,3 bar, insbesondere zwischen 0,5 und 50 bar vorzugsweise 1 bis 25 bar. Höhere transmembrane Drücke führen zumeist zu höheren Permeat- flüssen. Da der Syntheseaustrag zumeist direkt der Membranfiltrationsstufe mit den Synthesedruck zugeführt wird, kann der transmembrane Druck durch Anhebung des Permeatdruckes auf einen Wert abgesenkt werden, der kleiner als der Synthesedruck ist.The optimal transmembrane pressures between retentate and permeate are essentially dependent on the diameter of the membrane pores, the hydrodynamic conditions that influence the top layer structure and the mechanical stability of the membrane at the operating temperature, depending on the membrane type, at least 0.3 bar. in particular between 0.5 and 50 bar, preferably 1 to 25 bar. Higher transmembrane pressures mostly lead to higher permeate flows. Since the synthesis discharge is mostly fed directly to the membrane filtration stage with the synthesis pressure, the transmembrane pressure can be reduced to a value which is lower than the synthesis pressure by increasing the permeate pressure.
Da die Synthesetemperatur durch das Verfahren vorgegeben ist und über 80°C liegt, muss die Membran bei dieser Temperatur stabil sein. Höhere Temperaturen führen prinzipiell zu höheren Permeat- flüssen und sind daher bevorzugt.Since the synthesis temperature is determined by the process and is above 80 ° C, the membrane must be stable at this temperature. In principle, higher temperatures lead to higher permeate flows and are therefore preferred.
Falls bei speziellen Einsatzfällen des erfindungsgemäßen Verfahrens Membranen eingesetzt werden müssen, die bei diesen Temperaturen nicht stabil sind, muss die Reaktionsmischung vor der Filtration abgekühlt und das Retentat vor der Zuführung in den Reaktor wieder erhitzt werden. Diese Ausführungsform ist nicht bevorzugt .If membranes which are not stable at these temperatures have to be used in special applications of the process according to the invention, the reaction mixture has to be cooled before the filtration and the retentate has to be heated again before being fed into the reactor. This embodiment is not preferred.
Die erreichbaren Permeatflüsse sind stark von der eingesetzten Membranart und Membrangeometrie, von den Prozessbedingungen, von der Suspensionszusammensetzung, von der Katalysatorkonzentration und vom Katalysatortyp abhängig. Die Flüsse liegen üblicherweise zwischen 20 und 500 kg/m2/h.The permeate flows that can be achieved depend heavily on the membrane type and geometry used, on the process conditions, on the suspension composition, on the catalyst concentration and on the catalyst type. The rivers are usually between 20 and 500 kg / m2 / h.
Durch das erfindungsgemäße Verfahren kann eine Katalysatorrückhaltung > 99 % erzielt werden.A catalyst retention> 99% can be achieved by the process according to the invention.
Nach dem erfindungsgemäßen Verfahren lassen sich alle für die Hydrierung von Nitroaromaten einsetzbaren Katalysatoren abtrennen. Geeignete Katalysatoren sind Metalle der VIII. Nebengruppe des Periodensystems, die auf Trägermaterialien wie Kohlenstoff oder Oxiden des Aluminiums, des Siliciums oder anderer Materialien aufgebracht sein können. Vorzugsweise werden Raney- Nickel und/oder geträgerte Katalysatoren auf Basis von Nickel, Palladium, Iridium und/oder Platin auf Kohlenstoffträgern verwendet . Besonders vorteilhaft lässt sich das Verfahren zur Abtrennung von Katalysatoren einsetzen, an denen wenig der als Nebenprodukt bei der Hydrierung anfallenden hochkondensierten Nebenprodukte, häufig als "Teer" bezeichnet, anfallen. Dieser Teer kann zu Verblockungen der eingesetzten Membran führen und die Lebensdauer des Filters herabsetzen. Da Edelmetallkatalysatoren besonders selektiv arbeiten und bei der Hydrierung von Nitroaromaten nur sehr wenig höhermolekularen "Teer" erzeugen, ist die Abtrennung der Edelmetallkatalysatoren mittels Membranfiltration besonders vorteilhaft. Die mittlere Korngröße der eingesetzten Katalysatoren liegt zumeist im Bereich zwischen 10 nm und 200 μm, insbesondere im Bereich zwischen 50 nm und 100 Um und vorzugsweise zwischen 100 nm und 30 um.All of the catalysts which can be used for the hydrogenation of nitroaromatics can be separated off by the process according to the invention. Suitable catalysts are metals of subgroup VIII of the periodic table, which can be applied to support materials such as carbon or oxides of aluminum, silicon or other materials. Raney nickel and / or supported catalysts based on nickel, palladium, iridium and / or platinum on carbon supports are preferably used. The process can be used particularly advantageously for the separation of catalysts on which little of the highly condensed by-products obtained as a by-product in the hydrogenation, often referred to as "tar", is obtained. This tar can lead to blockages in the membrane used and reduce the service life of the filter. Since noble metal catalysts work particularly selectively and produce only very little higher molecular weight “tar” in the hydrogenation of nitroaromatics, the separation of the noble metal catalysts by means of membrane filtration is particularly advantageous. The average grain size of the catalysts used is usually in the range between 10 nm and 200 μm, in particular in the range between 50 nm and 100 μm and preferably between 100 nm and 30 μm.
Die Hydrierung der aromatischen Nitroverbindungen kann nach üblichen und bekannten Verfahren erfolgen.The aromatic nitro compounds can be hydrogenated by customary and known processes.
Dabei wird im Reaktor vorzugsweise, unabhängig von der Art der eingesetzten Nitroverbindungen, ein Druck von 5 bis 50 bar, bevorzugt 10 bis 30 bar, und eine Betriebstemperatur von 80 bis 200°C, bevorzugt 100 bis 180°C, aufrechterhalten.A pressure of 5 to 50 bar, preferably 10 to 30 bar, and an operating temperature of 80 to 200 ° C., preferably 100 to 180 ° C., is preferably maintained in the reactor, regardless of the type of nitro compounds used.
Die Mono- und/oder Polynitroverbindung kann hierbei in reiner Form, als Mischung mit dem entsprechenden Mono- und/oder Poly- amin, als Mischung mit dem entsprechenden Mono- und/oder Poly- amin und Wasser oder als Mischung mit dem entsprechenden Mono- und/oder Polyamin, Wasser und einem insbesondere alkoholischen Lösungsmittel eingesetzt. Die aromatische Mono- und/oder Poly- nitroverbindung wird fein verteilt in das Gemisch eingetragen. Das Reaktionsgemisch, welches den Reaktor verlässt, enthält Wasser, welches als Nebenprodukt bei der Hydrierung entsteht.The mono- and / or polynitro compound can be used in pure form, as a mixture with the corresponding mono- and / or polyamine, as a mixture with the corresponding mono- and / or polyamine and water or as a mixture with the corresponding mono- and / or polyamine, water and a particularly alcoholic solvent. The aromatic mono- and / or poly-nitro compound is introduced into the mixture in finely divided form. The reaction mixture which leaves the reactor contains water which is formed as a by-product of the hydrogenation.
Als Reaktoren werden die für die üblichen und bekannten Hydrier- reaktoren verwendet. Beispiele hierfür sind Rührkessel, Blasensäulen, die Packungen enthalten können, oder Schlaufenreaktoren, wie Loop-Venturi-Reaktoren, oder Strahlschlaufenreaktoren mit innerem und äußerem Kreislauf, wie beispielsweise in WO 00/35852 beschrieben.The reactors used are those for the customary and known hydrogenation reactors. Examples of this are stirred tanks, bubble columns, which can contain packings, or loop reactors, such as loop venturi reactors, or jet loop reactors with internal and external circuits, as described, for example, in WO 00/35852.
Besonders vorteilhaft kann das erfindungsgemäße Verfahren zur Abtrennung von Katalysatoren bei der Verwendung von Schlaufenreaktoren mit einem äußeren Kreislauf eingesetzt werden. Hierbei wird der Membranfilter im äußeren Kreislauf angeordnet.The process according to the invention for separating catalysts can be used particularly advantageously when using loop reactors with an external circuit. The membrane filter is arranged in the outer circuit.
In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird ein Hydrierreaktor eingesetzt, wie er in WO 00/35852 beschrieben ist. Bei dieser Ausführungsform kann auf eine zusätzliche Pumpe für die Membranfiltration verzichtet werden, da durch die Pumpe für den äußeren Kreislauf der notwendige Druck auf der Suspensionsseite gehalten werden kann. Dadurch kann das Verfahren deutlich vereinfacht werden. Außerdem ist bei der Verwendung derartiger Reaktoren ein vollständiger Umsatz der Nitroaromaten möglich, so dass sich die nachfolgende Aufarbeitung nach der vollständigen Abtrennung des Katalysators besonders einfach gestaltet . Bei diesem Verfahren kommen die Vorteile der Edelmetallkataysatoren, insbesondere solcher auf der Basis von Platin, Palladium und/oder Iridium, nämlich die hohe Aktivität und die gute Selektivität, besonders zum Tragen.In a particularly preferred embodiment of the process according to the invention, a hydrogenation reactor is used, as described in WO 00/35852. In this embodiment, an additional pump for membrane filtration can be dispensed with, since the pump for the external circuit can maintain the necessary pressure on the suspension side. This can significantly simplify the process. In addition, when such reactors are used, complete conversion of the nitroaromatics is possible, so that the subsequent workup is particularly simple after the catalyst has been completely removed. In this process, the advantages of precious metal catalysts, especially those on the Basis of platinum, palladium and / or iridium, namely the high activity and the good selectivity, especially for wearing.
Vorzugsweise werden im Rahmen des erfindungsgemäßen Verfahrens aromatische Nitrove bindungen mit einer oder mehreren Nitro- gruppen und 6 bis 18 C-Atomen, beispielsweise Nitrobenzole, wie o-, m-, p-Nitrobenzol, 1, 3-Dinitrobenzol, Nitrotoluole, wie z.B. 2,4-, 2 , 6-Dinitrotoluol, 2 , 4, 6-Trinitrotoluol, Nitroxylole, wie z.B. 1,2-Dirnethyl-3-, 1,2 Dirnethyl-4-, 1, 4-Dimethyl-2-, 1, 3-Dimethyl-2-, 2 , 4-Dimethyl-l- und 1, 3-Dimethyl-5-nitrobenzol, Nitronaphthaline, wie z.B. 1-, 2-Nitronaphthalin, 1,5 und 1,8-Di- nitronaphthalin, Chlornitrobenzole, wie z.B. 2-Chlor-l, 3-, l-Chlor-2 , 4-dinitrobenzol, o-, m-, p-Chlornitrobenzol , 1,2-Di- chlor-4-, l,4-Dichlor-2-, 2 , 4-Dichlor-l-und 1, 2-Dichlor-3-nitro- benzol, Chlornitrotoluole, wie z.B. 4-Chlor-2, 4-Chlor-3-, 2-Chlor-4- und 2-Chlor-6-nitrotoluol, Nitroaniline, wie z.B. o-, m-, p- Nitroanilin; Nitroalkohole, wie z.B. Tris (hydroxy- methyl)nitromethan, 2-Nitro-2-methyl-, 2-Nitro-2-ethyl-l, 3- propandiol, 2-Nitro-l-butanol und 2-Nitro-2-methyl-l-propanol sowie beliebige Gemische aus zwei oder mehreren der genannten Nitroverbindungen eingesetzt.Aromatic nitrove compounds having one or more nitro groups and 6 to 18 carbon atoms, for example nitrobenzenes, such as o-, m-, p-nitrobenzene, 1,3-dinitrobenzene, nitrotoluenes, such as e.g. 2,4-, 2,6-dinitrotoluene, 2,4,4-trinitrotoluene, nitroxylenes, e.g. 1,2-dimethyl-3-, 1,2-dimethyl-4-, 1,4-dimethyl-2-, 1,3-dimethyl-2-, 2,4-dimethyl-1- and 1,3-dimethyl 5-nitrobenzene, nitronaphthalenes, such as, for example 1-, 2-nitronaphthalene, 1,5 and 1,8-dinitronaphthalene, chloronitrobenzenes, e.g. 2-chloro-l, 3-, l-chloro-2, 4-dinitrobenzene, o-, m-, p-chloro-nitrobenzene, 1,2-di-chloro-4-, l, 4-dichloro-2-, 2 , 4-dichloro-1 and 1, 2-dichloro-3-nitrobenzene, chloronitrotoluenes, such as 4-chloro-2, 4-chloro-3-, 2-chloro-4- and 2-chloro-6-nitrotoluene, nitroanilines, e.g. o-, m-, p-nitroaniline; Nitro alcohols, e.g. Tris (hydroxymethyl) nitromethane, 2-nitro-2-methyl, 2-nitro-2-ethyl-l, 3-propanediol, 2-nitro-l-butanol and 2-nitro-2-methyl-l-propanol as well as any mixtures of two or more of the nitro compounds mentioned.
Bevorzugt werden nach dem erfindungsgemäßen Verfahren aromatische Nitroverbindungen, vorzugsweise Mononitrobenzol, Methylnitr- obenzol oder Methylnitrotoluol, und insbesondere 2,4-Dinitro- toluol oder dessen technische Gemische mit 2, 6-Dinitrotoluol, wobei diese Gemische vorzugsweise bis zu 35 Gewichtsprozent, bezogen auf das Gesamtgemisch, an 2, 6-Dinitrotoluol mit Anteilen von 1 bis 4 Prozent an vicinalem DNT und 0,5 bis 1,5 % an 2,5- und 3 , 5-Dinitrotoluol aufweisen, zu den entsprechenden Aminen hydriert .Aromatic nitro compounds, preferably mononitrobenzene, methylnitrosupenzene or methylnitrotoluene, and in particular 2,4-dinitro-toluene or its technical mixtures with 2,6-dinitrotoluene, are preferred according to the process of the invention, these mixtures preferably up to 35 percent by weight, based on the The total mixture, comprising 2, 6-dinitrotoluene with 1 to 4 percent of vicinal DNT and 0.5 to 1.5% of 2,5- and 3,5-dinitrotoluene, is hydrogenated to the corresponding amines.
Die Erfindung soll an dem nachfolgenden Beispiel näher erläutert werden.The invention is illustrated in the following example.
Beispiel 1 und Vergleichsbeispiel 2Example 1 and Comparative Example 2
Hydrierung von DinitrotoluolHydrogenation of dinitrotoluene
In einen 5-1-Strahlschlaufenreaktor mit Umwälzpumpe, Düse, Einsteckrohr und Wärmetauscher wurde Dinitrotoluol an einem geträgerten Nickelkatalysator mit einer mittleren Teilchengröße von 5 bis 10 μm bei 25 bar und 120°C hydriert. Die Aktivität des Katalysators wurde ständig anhand von Gaschromatographie- Proben verfolgt und wenn nötig, Katalysator nachdosiert. Die Konzentration des Katalysators betrug 3 Gew.-%, bezogen auf die Reaktionsmischung .Dinitrotoluene was hydrogenated on a supported nickel catalyst with an average particle size of 5 to 10 μm at 25 bar and 120 ° C in a 5-1 jet loop reactor with circulation pump, nozzle, plug-in pipe and heat exchanger. The activity of the catalyst was continuously monitored using gas chromatography samples and, if necessary, catalyst was added. The Concentration of the catalyst was 3% by weight, based on the reaction mixture.
Die Abtrennung des Katalysators aus der Reaktionsmischung konnte dabei wahlweise mit einem Membranfilter (erfindungsgemäß) oder einem Settier (Vergleich) erfolgen.The catalyst could be separated from the reaction mixture either with a membrane filter (according to the invention) or with a settier (comparison).
Beispiel 1 - MembranfiltrationExample 1 - Membrane Filtration
Ein aus hochporöser Keramik bestehender Zylinder mit einer Länge von 750 mm enthielt einen in Längsrichtung verlaufenden Kanal mit einem Durchmesser von 6 mm, auf dessen Oberfläche die eigentliche filterwirksame Membran aus Zirkoniumdioxid mit einer Porengröße von 50 nm aufgebracht war. Die zu behandelnde Suspension strömte mit einer Strömungsgeschwindigkeit von 4 m/s in dem Kanal entlang der Membran, wobei ein Teilstrom die Membran als Permeat passierte und durch das Keramik-Trägermaterial abgeführt wurde. Der Transmembrandruck betrug 2 bar, der Permeatfluss betrug 440 l/m2/h.A cylinder made of highly porous ceramic with a length of 750 mm contained a longitudinal channel with a diameter of 6 mm, on the surface of which the actual filter-effective membrane made of zirconium dioxide with a pore size of 50 nm was applied. The suspension to be treated flowed at a flow rate of 4 m / s in the channel along the membrane, a partial stream passing through the membrane as permeate and being discharged through the ceramic carrier material. The transmembrane pressure was 2 bar, the permeate flow was 440 l / m 2 / h.
Vergleichsbeispiel 2 - Schwerkraftabscheider (Settier)Comparative Example 2 - Gravity Separator (Settier)
Ein Teilstrom des Umwälzstromes (Reaktor-Umwälzpumpe-Düse) wurde mit dem Vordruck der Umwälzpumpe in den unteren Teil eines Settiers abgezweigt und von dort mengengeregelt ohne zusätzliches Förderorgan zurück in den Reaktor geschleust.A partial flow of the circulation flow (reactor-circulation pump-nozzle) was branched off with the admission pressure of the circulation pump into the lower part of a settier and from there was quantity-controlled and fed back into the reactor without additional conveying device.
Der eigentliche Reaktoraustrag (Settleraustrag) durchströmte aufwärts ein um 55° geneigtes Abscheiderrohr und wurde, gesteuert vom Flüssigkeitsstand beziehungsweise Gasgehalt im Reaktor, über ein Entspannungs entil ausgetragen. Die Strömungsverhältnisse in der Abscheiderlamelle waren so eingestellt, dass alle Partikel, die größer als 1 μm waren, abgeschieden wurden und in den Settiersumpf absanken, wo sie mit dem Kreislaufström (Settlerrück- führung) wieder in den Reaktor transportiert wurden. Kleinere Teilchen wurden mit dem Endprodukt ausgeschleust.The actual reactor discharge (settler discharge) flowed upwards through a separator pipe inclined by 55 ° and, controlled by the liquid level or gas content in the reactor, was discharged via an expansion valve. The flow conditions in the separator lamella were set in such a way that all particles larger than 1 μm were separated and sank into the settling sump, where they were transported back into the reactor with the recycle stream (settler return). Smaller particles were removed with the end product.
ErgebnisseResults
In zwei Versuchsreihen wurde der Reaktor einmal mit Schwerkraftabscheider (Vergleichsversuch) und einmal mit Membranfiltration (erfindungsgemäß) betrieben.In two test series, the reactor was operated once with a gravity separator (comparative test) and once with membrane filtration (according to the invention).
Mit Schwerkraftabscheider konnte über eine Periode von 4 Wochen eine Raum-Zeit-Ausbeute von 250-350 kg TDA/(m3-h) erreicht werden. Es wurden 400-600g Katalysator pro Tonne TDA verbraucht. Mit Membranfiltration wurde über eine Periode von 3 Monaten eine Raum-Zeit-Ausbeute von 400 bis 500 kg TDA/(m3-h) erreicht. Es wurden 350 bis 450 g Katalysator pro Tonne TDA verbraucht.With gravity separators, a space-time yield of 250-350 kg TDA / (m 3 -h) could be achieved over a period of 4 weeks. 400-600 g of catalyst were used per ton of TDA. With membrane filtration, a space-time yield of 400 to 500 kg TDA / (m 3 -h) was achieved over a period of 3 months. 350 to 450 g of catalyst were used per ton of TDA.
Beispiele 3 und 4Examples 3 and 4
Es wurden die in Beispiel 1 beschriebene Vorrichtungen zur Hydrierung und zur Katalysatorabtrennung eingesetzt und die Wirksamkeit unterschiedlicher Katalysatoren bei unterschiedlicher Reaktionstemperatur bei der Hydrierung von Nitrobenzol geprüft.The devices for hydrogenation and catalyst separation described in Example 1 were used and the effectiveness of different catalysts at different reaction temperatures in the hydrogenation of nitrobenzene was tested.
Beispiel 3Example 3
Es wurde der Katalysator aus Beispiel 1 in einer Konzentration von 2 Gew.-%, bezogen auf die Reaktionsmischung, eingesetzt. Der Transmembrandruck betrug 1 bar, der Permeatfluss betrug 200 l/m2/h.The catalyst from Example 1 was used in a concentration of 2% by weight, based on the reaction mixture. The transmembrane pressure was 1 bar, the permeate flow was 200 l / m 2 / h.
Bei 140°C konnte eine Raum-Zeit-Ausbeute von 800 kg/(m3-h) erreicht werden mit einer Selektivität 99,7 %, bei 180°C konnte eine Raum-Zeit-Ausbeute von 1800 kg/(m3-h) mit einer Selektivität 98,3 % erreicht werden.At 140 ° C a space-time yield of 800 kg / (m 3 -h) could be achieved with a selectivity of 99.7%, at 180 ° C a space-time yield of 1800 kg / (m 3 - h) 98.3% can be achieved with a selectivity.
Beispiel 4Example 4
Es wurde ein Katalysator aus 5 Gew.-% Platin und 2 Gew.-% Eisen auf Aktivkohle mit einer mittleren Teilchengröße von 20 bis 30 μm in einer Konzentration von 2 Gew.-%, bezogen auf die Reaktionsmischung, eingesetzt. Der Transmembrandruck betrug 1 bar, der Permeatfluss betrug 200 l/m2/h.A catalyst consisting of 5% by weight of platinum and 2% by weight of iron on activated carbon with an average particle size of 20 to 30 μm in a concentration of 2% by weight, based on the reaction mixture, was used. The transmembrane pressure was 1 bar, the permeate flow was 200 l / m 2 / h.
Bei 140°C konnte eine Raum-Zeit-Ausbeute von 1500 kg/(m3-h) mit Selektivität 99,82 % erreicht werden. Bei 180°C konnte eine Raum- Zeit-Ausbeute von 2200 kg/(m3-h) mit einer Selektivität 99,6 % erreicht werden. At 140 ° C, a space-time yield of 1500 kg / (m 3 -h) with selectivity 99.82% could be achieved. At 180 ° C, a space-time yield of 2200 kg / (m 3 -h) could be achieved with a selectivity of 99.6%.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Aminen durch katalytische Hydrierung von Nitroaromaten und nachfolgende Abtrennung der Katalysatoren aus dem Reaktionsgemisch, enthaltend mindestens ein aromatisches Amin und Wasser, dadurch gekennzeichnet, dass die Abtrennung der Katalysatoren mittels Membranfiltration erfolgt, wobei die Membranfiltration bei einem Druck auf der Suspensionsseite von 5 bis 50 bar, einer Druckdifferenz zwischen der Suspensionsseite und der Permeatseite von mindestens 0,3 bar und einer Strömungsgeschwindigkeit auf der Suspensionsseite von 1 bis 6 m/s durchgeführt wird.1. A process for the preparation of amines by catalytic hydrogenation of nitroaromatics and subsequent separation of the catalysts from the reaction mixture containing at least one aromatic amine and water, characterized in that the separation of the catalysts takes place by means of membrane filtration, the membrane filtration being carried out at a pressure on the suspension side from 5 to 50 bar, a pressure difference between the suspension side and the permeate side of at least 0.3 bar and a flow velocity on the suspension side from 1 to 6 m / s.
2. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass der Druck auf der Suspensionsseite 10 bis 30 bar beträgt.2. The method according to claim 1, characterized in that the pressure on the suspension side is 10 to 30 bar.
3. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Filtration kontinuierlich durchgeführt wird.3. The method according to claim 1, characterized in that the filtration is carried out continuously.
4. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Filtration diskontinuierlich durchgeführt wird.4. The method according to claim 1, characterized in that the filtration is carried out batchwise.
5. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Filtermembran einen Porendurchmesser im Bereich zwischen5. The method according to claim 1, characterized in that the filter membrane has a pore diameter in the range between
10 nm und 20 Um aufweist.10 nm and 20 µm.
6. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Hydrierung in einem Strahlschlaufenreaktor durchgeführt wird.6. The method according to claim 1, characterized in that the hydrogenation is carried out in a jet loop reactor.
7. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Hydrierung in einem Strahlschlaufenreaktor mit äußerem und innerem Kreislauf durchgeführt wird.7. The method according to claim 1, characterized in that the hydrogenation is carried out in a jet loop reactor with an external and internal circuit.
8. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass als8. The method according to claim 1, characterized in that as
Katalysatoren solche eingesetzt werden, die Metalle der VIII. Nebengruppe des Periodensystems auf Trägern enthalten.Catalysts are used which contain metals of subgroup VIII of the periodic table on supports.
9. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass als Katalysatoren Platin, Palladium und/oder Iridium enthaltende9. The method according to claim 1, characterized in that as catalysts containing platinum, palladium and / or iridium
Katalysatoren auf Kohlenstoffträgem eingesetzt werden.Catalysts on carbon supports are used.
10. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass die Hydrierung in einem Strahlschlaufenreaktor mit äußerem und innerem Kreislauf durchgeführt wird, als Katalysatoren10. The method according to claim 1, characterized in that the hydrogenation is carried out in a jet loop reactor with an external and internal circuit, as catalysts
Platin, Palladium und/oder Iridium enthaltende Katalysatoren auf Kohlenstoffträgern eingesetzt werden und der Membranfilter im äußeren Kreislauf des Reaktors angeordnet ist. Catalysts containing platinum, palladium and / or iridium be used on carbon supports and the membrane filter is arranged in the outer circuit of the reactor.
EP03714720A 2002-02-06 2003-01-30 Method for the production of amines Expired - Lifetime EP1474378B1 (en)

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Families Citing this family (15)

* Cited by examiner, † Cited by third party
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DE102005008613A1 (en) * 2005-02-23 2006-08-31 Basf Ag Preparation of e.g. aromatic amines comprises hydrogenating nitro-aromatic compounds in presence of catalyst, separating catalyst and measuring absorption of UV/visible radiation to determine concentrations of nitro and nitroso compounds
CN101205189B (en) * 2006-12-15 2013-06-12 住友化学株式会社 Preparation method of aromatic amine and reaction device
US20090280262A1 (en) * 2008-05-08 2009-11-12 Chung Yuan Christian University Method for forming composite membrane with porous coating layer and apparatus thereof
JP2012526085A (en) * 2009-05-07 2012-10-25 ビーエーエスエフ ソシエタス・ヨーロピア Method for producing aromatic amine and apparatus for producing the same
KR101770439B1 (en) 2010-01-14 2017-08-22 바이엘 인텔렉쳐 프로퍼티 게엠베하 Method for producing aromatic amines in the liquid phase
HUE037511T2 (en) * 2010-05-17 2018-09-28 Basf Se Process for the preparation of tuluenediamine by hydrogenation of dinitrotoluene
US8981155B2 (en) 2010-12-06 2015-03-17 Basf Se Process for preparing aromatic amines
KR20130136502A (en) 2010-12-06 2013-12-12 바스프 에스이 Method for producing aromatic amines
DE102011082441A1 (en) 2011-09-09 2013-03-14 Evonik Oxeno Gmbh Jet loop reactor with nanofiltration
EP2757088B1 (en) * 2013-01-22 2016-08-03 Covestro Deutschland AG Method for manufacturing aromatic amines
EP3181220A1 (en) * 2015-12-16 2017-06-21 Basf Se A process for removing a heterogeneous catalyst from a reaction product and a process for producing an aromatic amine
HUE053603T2 (en) 2016-10-10 2021-07-28 Basf Se Catalyst modification with alkaline metal, alkaline earth metal or rare earth metal ions in continuous liquid phase hydration of nitro compounds
US11339115B2 (en) 2017-10-16 2022-05-24 Basf Se Increasing the catalyst selectivity in the continuous hydrogenation of nitro compounds by adding ammonia
CN110756120A (en) * 2018-07-27 2020-02-07 上海凯鑫分离技术股份有限公司 Continuous hydrogenation reaction device and reaction process
CN111718266A (en) * 2019-03-20 2020-09-29 中石化南京化工研究院有限公司 Purification method and application of p-nitroaniline

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2835943A1 (en) * 1978-08-17 1980-03-20 Heyl & Co Polymeric soluble hydrogenation catalyst - contg. iron, cobalt, nickel or platinum gp. metal as covalent or coordination cpd. with soluble polymer
DE3040631A1 (en) * 1980-10-29 1982-05-27 Merck Patent Gmbh, 6100 Darmstadt METHOD FOR SEPARATING METAL CATALYSTS AND USE OF MEMBRANE SEPARATING DEVICES
DE3245318C3 (en) 1982-12-08 1996-06-20 Bayer Ag Process for carrying out pressure reactions with suspended catalysts
DE4323687A1 (en) 1993-07-15 1995-01-19 Bayer Ag Continuous process for the production of aromatic amines
JP4293732B2 (en) * 1998-12-12 2009-07-08 ビーエーエスエフ ソシエタス・ヨーロピア Amine production method
CN1328244C (en) * 2002-03-15 2007-07-25 南京工业大学 Process for producing para-amino-phenol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03066571A1 *

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DE50301146D1 (en) 2005-10-13
AU2003218967A1 (en) 2003-09-02
ATE303984T1 (en) 2005-09-15
CN1312108C (en) 2007-04-25
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US20050177003A1 (en) 2005-08-11
JP2006508017A (en) 2006-03-09

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